Plasticized vinyl chloride polymers



UNITED STATE PATENT orrlcr.

PLASTICIZED VINYL CHLORIDE POLYMERS Joachim Dani, Dayton, Ohio, assignorto Moncanto Chemical Company, St. Louis, Mo a corporation of Delaware NoApplication May erial No.

6 Claims. (01. 260-303) flail invention relates to compositions usefulas plasticizers, particularly in vinyl chloride resins. Moreparticularly the invention relates to plasticiaed vinyl chloride resinsmade by the incorporation of the esters.

The primary purpose of this invention is to provide new plasticizedcompositions having improved permarience. A further purpose of thisinvention is to provide useful general purpose plasticizers. A stillfurther purpose of this in- Yention is to provide a method of preparingcompolitions from vinyl chloride polymers.

It has been found that esters of the phenylbenzoic acids and aliphatichydrocarbon alcohols, aliphatic oxa-hydrocarbon alcohols, and allphaticthia-hydrocarbon alcohols having from 8 to 14 carbon, oxygen and sulfuratoms are excellent plasticizers for vinyl chloride polymers and thecompositions made by the incorporation of theplasticizers in vinylchloride resins have unusual low temperature flexibility and desirablelow volatility. Suitable esters are the 2-ethylhexyl m-phenylbenzoate,the corresponding paraand ortho-phenylbenzoates, or mixtures thereof,and the various phenylbenzoates of n-hexyl, 2- methylheptyl, dodecyl,dimethylheptyl, 2-butoxyethyl, 2-thia-n-heptyl and isooctyl alcohols,butyl carbitol, and other homologous straight and branched alcoholshaving 8 to 14 atoms, including those having oxygen or divalent sulfuratoms substituted for methylene radicals in the radical chains.

The esters are valuable plasticizers for polyvinyl chloride andcopolymers of more than 70 percent of vinyl chloride and up to 30percent of other polymefrizable monomers copolymerized therewith, forexample vinyl acetate and other vinyl esters of monocarboxylic acids,ethyl maleate, ethyl fumarate and other alkyl esters of maleic andfumaric acids.

The plasticizers are blended with the vinyl resin in the conventionalmanner, for example by mixing on a roll mill, a Banbury W'D mixer or anyother suitable mixing device. The plasticiaers are used in proportionsnecessary to achieve the desired plasticity. Although the quantity ofplasticizer will depend upon the particular polymer to be plasticizedand upon its molecular weight it is generally found that from 5 to 50percent of plasticizer will in most cases produce a satisfactorycomposition for general utility. Such quantity of plasticizer willgenerally remain as a permanent part of the vinyl rain and the modifiedvinyl resin so prepared will not deteriorate or become embrittled byrea- W son of the loss of the plasticizer during use.

The value of the plasticizers are estimated by three tests (1)compatibility (2) volatility and '(3) Clash-Berg flex temperature. Thecompatibility is determined by visual inspection, clarity being arequisite in most applications for vinyl chloride polymers. Thevolatility is estimated by the test of heating at 105 C. for 24 hoursand measuring the percentage of the plasticizers evaporated by loss ofweight. The Clash-Berg flex temperature is determined by cooling thepolymer sample to about C. and observing the change in the modulus ofrigidity as the sample warms up to room temperature, the flextemperature being that at which the modulus of rigidity is 135,000pounds per square inch. Of these tests the compatibility is of primaryimportance while the others are only critical for certain applications.If the polymer is to be subjected to outside weather conditions flextemperatures of -20 to -30 C. are desirable, otherwise 0" C. issatisfactory. If the polymer is to be subjected to elevated temperaturesa volatility of 5 to 10 percent is advantageous, otherwise volatilitiesas high as 25 percent are often not objectionable. The volatilities andflex temperature, of polymer plasticizer blends are dimcult to predictand often have no apparent relationship to the physical constants of theplasticizer.

The new plasticizers are of general utility in softening vinyl chloridepolymers. They may be used as the only plasticizing component in acompounded vinyl chloride polymer or they may be used in conjunctionwith other plasticizers.

Further details of the practice of this invention are set forth withrespect to the following speciflc examples.

Example 1 The butoxyethyl ester of phenylbenzoic acid was evaluated as aplasticizer by milling 40 parts by weight thereof and parts of polyvinylchloride and one part of a standard commercially available stabilizer.The thoroughly milled samples were molded into apropriate test piecesand tested by means of the Clash-Berg flex temperature procedure and forvolatility. The compositions were found to have flex temperatures of -24C. and a volatility of 7.2 percent.

Example 2 Using the procedure described in the precedin: example thez-ethylhexyl esters of phenylbenzoic acid was evaluated. It was found tohave 3 a flex temperature of 25 C. and a volatility of 8.9 percent.

Although the invention has been described with respect to specificembodiments, it is not intended that the details thereof shall beconstrued as limitations upon the scope of the invention except to theextent incorporated in the following claims.

What is claimed is:

l. A plasticized vinyl resin composition which comprises a vinylchloride polymer containing intimately dispersed therein an ester of aphenylbenzoic acid and an aliphatic monohydric aicohol of the groupconsisting of hydrocarbon alcohols, oxa-hydrocarbon alcohols,thia-hydrocarbon alcohols, said alcohols having the total of 8 to 14carbon, oxygen and sulfur atoms.

2. A vinyl resin composition which comprises polyvinyl chloride havingintimately dispersed therein from 5 to 50 percent of an ester of aphenylbenzolc acid and an aliphatic alcohol of the group consisting ofhydrocarbon alcohols, oxa-hydrocarbon alcohols, thia-hydrocarbonalcohols, said alcohols having the total of 8 to 14 carbon, oxygen andsulfur atoms.

3. A vinyl chloride resin which comprises a copolymer of at least 70percent of vinyl chloride and up to 30 percent of a monomer of the groupconsisting of vinyl acetate, ethyl maleate and ethyl fumarate, saidcopolymers having intimately dispersed therein from 5 to 50 percent of 4anesteroraphenylbensoic acidandanaliphatic monohydric alcohol of thegroup comisting of hydrocarbon alcohols, oxa-hydrocarbon alcohols,thia-hydrocarbon alcohols, said alcohols having a total or 8 to 14carbon, oxygen and sulfur atoms.

4. A vinyl resin composition which comprises polyvinyl chloride havingintimately dispersed therein from 5 to percent of 2-ethylhexylmphenylbenzoate.

5. A vinyl resin composition which comprises a copolymer of at leastpercent of vinyl chloride and up to 30 percent of ethyl maleate, saidcopolymers containing intimately dispersed therein from 5 to 50 percentof n-butoxyethyi m-phenylbenzoate.

6. A vinyl resin composition which comprises a copolymer of at least '70percent of vinyl chloride and up to 30 percent of ethyl maleate, saidcopolymers containing intimately dispersed therein from 5 to 50 percentof Z-ethylhexyl meta-phenylbenzoate.

J OACHIM DAZZI.

REFERENCES CITED UNITED s'ra'rns P'A'mN'm Name Date Kilgore May 22, 1948Number

2. A VINYL RESIN COMPOSITION WHICH COMPRISES POLYVINYL CHLORIDE HAVINGINTIMATELY DISPERSED THEREIN FROM 5 TO 50 PERCENT OF AN ESTER OF APHENYLBENZOIC ACID AND AN ALIPHATIC ALCOHOL OF THE GROUP CONSISTING OFHYDROCARBON ALCOHOLS, OXA-HYDROCARBON ALCOHOLS, THIA-HYDROARBONALCOHOLS, SAID ALCOHOLS HAVING THE TOTAL OF 8 TO 14 CARBON, OXYGEN ANDSULFUR ATOMS.